EP0027209A1 - N,N-dimethyl-N'-isobutyl-N'-beta-hydroxyethyl 1,3-propylene diamine, and process for its preparation - Google Patents
N,N-dimethyl-N'-isobutyl-N'-beta-hydroxyethyl 1,3-propylene diamine, and process for its preparation Download PDFInfo
- Publication number
- EP0027209A1 EP0027209A1 EP80105942A EP80105942A EP0027209A1 EP 0027209 A1 EP0027209 A1 EP 0027209A1 EP 80105942 A EP80105942 A EP 80105942A EP 80105942 A EP80105942 A EP 80105942A EP 0027209 A1 EP0027209 A1 EP 0027209A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- isobutyl
- dimethyl
- propylenediamine
- hydroxyethyl
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002262 Schiff base Substances 0.000 claims abstract description 7
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 7
- WIZWZYYLUUGFNZ-UHFFFAOYSA-N 1-n,1-n-dimethyl-2-n-(2-methylpropyl)propane-1,2-diamine Chemical compound CC(C)CNC(C)CN(C)C WIZWZYYLUUGFNZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical class CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- JUWUSARQMNEEFZ-UHFFFAOYSA-N 2-[1-(dimethylamino)propan-2-yl-(2-methylpropyl)amino]ethanol Chemical compound CC(C)CN(CCO)C(C)CN(C)C JUWUSARQMNEEFZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 hydroxyethyl group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- BUHYMJLFRZAFBF-UHFFFAOYSA-N 3,4,5-trimethoxybenzoyl chloride Chemical compound COC1=CC(C(Cl)=O)=CC(OC)=C1OC BUHYMJLFRZAFBF-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000006547 Leuckart Thiophenol synthesis reaction Methods 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
Definitions
- the invention relates to the chemical compound N, N-dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylenediamine, a process for its preparation and its use.
- DE-OS 26 25 684 describes a process for accelerating addition and polymerization reactions of organic isocyanates by basic catalysis.
- hydroxyalkyl tert-amines with at least one primary hydroxyethyl group of the general formula are used as catalysts With Application.
- the invention consists in the chemical compound N, N-dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylenediamine.
- the new compound can be prepared in a three-stage synthesis which proceeds with high selectivity.
- dimethylaminopropylamine and isobutyraldehyde are converted to the corresponding Schiff base. Both starting materials are available on an industrial scale and the reaction takes place with high selectivity. Although dimethylaminopropylamine is a strong base, the isobutyraldehyde surprisingly does not undergo aldol condensation; neither isobutyraldol nor other by-products are formed.
- the Schiff base resulting from the reaction of amine and aldehyde is then hydrogenated to N, N-dimcthyl-N'-isobutyl-propylenediamine in the second reaction step.
- the reaction with hydrogen can be carried out by methods known for Schiff bases.
- Nickel catalysts with a nickel content of 30 to 50% by weight and supports such as silica, aluminum oxide or aluminum silicates have proven particularly useful.
- the reaction is usually carried out at 80-130 ° C. and 80-120 bar.
- the substituted propylenediamine is reacted with ethylene oxide.
- the ethylene oxide is expediently added in the presence of a strongly acidic ion exchanger, at temperatures between 80 and 150 ° C. and pressures of 0-20 bar. Under these conditions the reaction proceeds with a selectivity of 80 - 90% based on the substituted hydroxylamine.
- the new compound has proven to be an excellent catalyst for the production of polyurethane resins from isocyanates and compounds with a mobile hydrogen atom. In this field of application it can be used both alone and together with other tertiary amines or with organometallic compounds.
- the A r t of the reaction components is subject here to any restriction.
- isocyanates can be reacted with all polyols which are used to prepare polyurethanes in the presence of the compound according to the invention as a catalyst.
- Suitable polyhydric alcohols are glycol, glycerin and higher polyols, if these contain other functional groups, for example sucrose and aminopolyols.
- the hydroxy function of the polyol can be primary or secondary, or a mixture of both. In general, any polyol can be used which has at least two active hydrogen atoms.
- the new compound in addition to being a catalyst in the production of polyurethanes, the new compound can also be used as a valuable intermediate in the synthesis of pharmaceuticals.
- the reaction with 3,4,5-trimethoxybenzoyl chloride leads to an ester with cardioactive properties.
Abstract
Gegenstand der Erfindung ist die neue Verbindung N,N-Dimethyl-N'-isobutyl-N'-β-hydroxyethyl-propylendiamin, die als Katalysator zur Herstellung von Polyurethanen und als Zwischenprodukt bei der Synthese von Pharmazeutika eingesetzt werden kann. Ein Verfahren zur Herstellung der neuen Verbindung geht von Dimethylaminopropylamin aus, das mit Isobutyraldehyd umgesetzt wird. Die resultierende Schiff'sche Base wird zu N,N-Dimethyl-N'-isobutyl-propylendiamin hydriert, das man schließlich mit Ethylenoxid zu der erfindungsgemäßen Verbindung umsetzt.The invention relates to the new compound N, N-dimethyl-N'-isobutyl-N'-β-hydroxyethyl-propylenediamine, which can be used as a catalyst for the production of polyurethanes and as an intermediate in the synthesis of pharmaceuticals. A process for the preparation of the new compound starts from dimethylaminopropylamine, which is reacted with isobutyraldehyde. The resulting Schiff base is hydrogenated to N, N-dimethyl-N'-isobutyl-propylenediamine, which is finally reacted with ethylene oxide to give the compound of the invention.
Description
Die Erfindung betrifft die chemische Verbindung N,N-Dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylendiamin, ein Verfahren zu ihrer Herstellung und ihre Verwendung.The invention relates to the chemical compound N, N-dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylenediamine, a process for its preparation and its use.
Es ist bekannt, daß die Addition von Verbindungen mit beweglichem Wasserstoff an Isocyanate, die zu Polyurethanen führt durch tertiäre Amine katalysiert wird. Auch bestimmte tertiäre Hydroxyalkylamine wurden als Katalysatoren für die Herstellung von Polyurethanen aus den genannten Ausgangsstoffen beschrieben. So kann man für diesen Zweck z.B. Dimethyläthanolamin verwenden. Als nachteilig erweist es sich jedoch, daß diese Verbindung ziemlich flüchtig ist und schlechtes Gelbildungs- und Härtungsvermögen besitzt. Daher setzt man Dimethyläthanolamin im allgemeinen nur als Co-Katalysator zusammen mit anderen Katalysatoren ein.It is known that the addition of compounds with mobile hydrogen to isocyanates, which leads to polyurethanes, is catalyzed by tertiary amines. Certain tertiary hydroxyalkylamines have also been described as catalysts for the production of polyurethanes from the starting materials mentioned. For example, for this purpose Use dimethylethanolamine. However, it turns out to be disadvantageous that this compound is rather volatile and has poor gelation and curing properties. Therefore, dimethylethanolamine is generally used only as a co-catalyst together with other catalysts.
In der DE-OS 26 25 684 ist ein Verfahren zur Beschleunigung von Additions- und Polymerisationsreaktionen organischer Isocyanate durch basische Katalyse beschrieben.DE-OS 26 25 684 describes a process for accelerating addition and polymerization reactions of organic isocyanates by basic catalysis.
Als Katalysator finden bei dieser Arbeitsweise Hydroxyalkyl-tert.-amine mit wenigstens einer primären Hydroxy- äthylgruppe der allgemeinen Formel
Diese Verbindungen eignen sich zwar als Katalysatoren für die Herstellung von Polyurethanen aus Isocyanaten. Ihre Herstellung nach der Leuckart -Synthese durch Umsetzung von Aminen mit Aldehyden oder Ketonen durch Erhitzen mit Ameisensäure ist aber technisch aufwendig und, bedingt durch den erforderlichen hohen Ameisensäure- Überschuß und eine umständliche Aufarbeitung des Reaktionsprodukts nicht immer wirtschaftlich durchzuführen.These compounds are suitable as catalysts for the production of polyurethanes from isocyanates. Their preparation according to the Leuckart synthesis by reacting amines with aldehydes or ketones by heating with formic acid is technically complex and, due to the high excess of formic acid required and the laborious work-up of the reaction product, is not always economical.
Es bestand daher die Aufgabe, einen leicht herzustellenden Katalysator für die Addition von Verbindungen mit beweglichem Wasserstoff an Isocyanate zu entwickeln, der großtechnisch auf einfache Art und Weise herstellbar ist.It was therefore the task of developing an easy-to-produce catalyst for the addition of compounds with mobile hydrogen to isocyanates, which can be prepared on a large industrial scale in a simple manner.
Die Erfindung besteht in der chemischen Verbindung N,N-Dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylendiamin.The invention consists in the chemical compound N, N-dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylenediamine.
Die Herstellung der neuen Verbindung kann erfindungsgemäß in einer dreistufigen mit hoher Selektivität ablaufenden Synthese erfolgen.According to the invention, the new compound can be prepared in a three-stage synthesis which proceeds with high selectivity.
Im ersten Reaktionsschritt werden Dimethylaminopropylamin und Isobutyraldehyd zur entsprechenden Schiff'schen Base umgesetzt. Beide Ausgangsstoffe sind großtechnisch verfügbar und die Reaktion erfolgt mit hoher Selektivität. Obgleich Dimethylaminopropylamin eine starke Base ist, geht der Isobutyraldehyd überraschenderweise keine Aldolkondensation ein; weder Isobutyraldol noch andere Nebenprodukte werden gebildet.In the first reaction step, dimethylaminopropylamine and isobutyraldehyde are converted to the corresponding Schiff base. Both starting materials are available on an industrial scale and the reaction takes place with high selectivity. Although dimethylaminopropylamine is a strong base, the isobutyraldehyde surprisingly does not undergo aldol condensation; neither isobutyraldol nor other by-products are formed.
Die aus der Umsetzung von Amin und Aldehyd resultierende Schiff'sche Base wird darauf im zweiten Reaktionsschritt zu N,N-Dimcthyl-N'-isobutyl-propylendiamin hydriert. Die Umsetzung mit Wasserstoff kann nach für Schiff'sche Basen bekannten Verfahren erfolgen. Besonders bewährt haben sich Nickelkatalysatoren mit einem Nickelgehalt von 30 bis 50 Gewichts-% und Trägern wie Kieselsäure, Aluminiumoxid oder Aluminiumsilikaten. Die Reaktion wird üblicherweise bei 80 - 130 °C und)80 - 120 bar durchgeführt.The Schiff base resulting from the reaction of amine and aldehyde is then hydrogenated to N, N-dimcthyl-N'-isobutyl-propylenediamine in the second reaction step. The reaction with hydrogen can be carried out by methods known for Schiff bases. Nickel catalysts with a nickel content of 30 to 50% by weight and supports such as silica, aluminum oxide or aluminum silicates have proven particularly useful. The reaction is usually carried out at 80-130 ° C. and 80-120 bar.
Schließlich wird im dritten Reaktionsschritt zur Einführung einer Hydroxyethylgruppe in das Molekül das substituierte Propylendiamin mit Ethylenoxid umgesetzt. Die Addition des Ethylenoxids erfolgt zweckmäßig in Gegenwart eines stark sauren Ionenaustauschers, bei Temperaturen zwischen 80 und 150 °C und Drücken von 0 - 20 bar. Unter diesen Bedingungen verläuft die Reaktion mit einer Selektivität von 80 - 90% bezogen auf das substituierte Hydroxylamin.Finally, in the third reaction step to introduce a hydroxyethyl group into the molecule, the substituted propylenediamine is reacted with ethylene oxide. The ethylene oxide is expediently added in the presence of a strongly acidic ion exchanger, at temperatures between 80 and 150 ° C. and pressures of 0-20 bar. Under these conditions the reaction proceeds with a selectivity of 80 - 90% based on the substituted hydroxylamine.
Die neue Verbindung hat sich als ausgezeichneter Katalysator für die Herstellung von Polyurethanharzen aus Isocyanaten und Verbindungen mit beweglichem Wasserstoffatom erwiesen. Auf diesem Anwendungsgebiet kann sie sowohl allein als auch zusammen mit anderen tertiären Aminen oder mit metallorganischen Verbindungen verwendet werden. Die Art der Reaktionskomponenten unterliegt hierbei keiner Beschränkung. So kann man Isocyanate mit allen Polyolen, die zur Herstellung von Polyurethanen verwendet werden in Gegenwart der erfindungsgemäßen Verbindung als Kata- lysator umsetzen. Geeignete, mehrwertige Alkohole sind Glykol, Glycerin und höhere Polyole, aucwenn diese andere funktionelle Gruppen enthalten, z.B. Saccharose und Aminopolyole. Die Hydroxyfunktion des Polyols kann primär oder sekundär oder ein Gemisch von beiden sein. Im allgemeinen kann jedes Polyol verwendet werden, das wenigstens zwei aktive Wasserstoffatome aufweist.The new compound has proven to be an excellent catalyst for the production of polyurethane resins from isocyanates and compounds with a mobile hydrogen atom. In this field of application it can be used both alone and together with other tertiary amines or with organometallic compounds. The A r t of the reaction components is subject here to any restriction. For example, isocyanates can be reacted with all polyols which are used to prepare polyurethanes in the presence of the compound according to the invention as a catalyst. Suitable polyhydric alcohols are glycol, glycerin and higher polyols, if these contain other functional groups, for example sucrose and aminopolyols. The hydroxy function of the polyol can be primary or secondary, or a mixture of both. In general, any polyol can be used which has at least two active hydrogen atoms.
Außer als Katalysator bei der Herstellung von Polyurethanen kann die neue Verbindung auch als ein wertvolles Zwischenprodukt bei der Synthese von Pharmazeutika eingesetzt werden. So führt die Umsetzung mit 3,4,5-Trimethoxybenzoylchlorid zu einem Ester mit kardioaktiven Eigenschaften.In addition to being a catalyst in the production of polyurethanes, the new compound can also be used as a valuable intermediate in the synthesis of pharmaceuticals. The reaction with 3,4,5-trimethoxybenzoyl chloride leads to an ester with cardioactive properties.
In den folgenden Beispielen sind die Herstellung der neuen Verbindung und ihre physikalischen Eigenschaften näher beschrieben.The preparation of the new compound and its physical properties are described in more detail in the following examples.
Herstellung der Schiff'schen Base aus Dimethylaminopropylamin (DMAPA) und Isobutyraldehyd.Preparation of Schiff's base from dimethylaminopropylamine (DMAPA) and isobutyraldehyde.
Zu 1 020 g (10 Mol) DMAPA in einem 4-1-Dreihalskolben werden unter Rühren innerhalb von 2 Stunden 721 g (10 Mol) Isobutyraldehyd tropfenweise zugesetzt. Durch Kühlung hält man die Reaktionstemperatur unterhalb 30 °C. Während der 120 Min. dauernden Nachreaktion beträgt die Temperatur etwa 20 °C. Nach Beendigung der Reaktion liegt ein 2-Phasen-System vor. Die wäßrige Phase, die nahezu der stöchiometrisch zu erwartenden Menge Wasser entspricht, wird abgetrennt und die organische Phase der katalytischen Hydrierung zugeführt.721 g (10 mol) of isobutyraldehyde are added dropwise to 1 020 g (10 mol) of DMAPA in a 4-1 three-necked flask with stirring over the course of 2 hours. The reaction temperature is kept below 30 ° C. by cooling. During the post-reaction lasting 120 minutes, the temperature is about 20 ° C. After the reaction has ended, a 2-phase system is available. The aqueous phase, which corresponds almost to the stoichiometric amount of water to be expected, is separated off and the organic phase is fed to the catalytic hydrogenation.
Umsatz: 90 %Turnover: 90%
Ausbeute: 1 451 g (93 % d. Th.)Yield: 1 451 g (93% of theory)
Katalytische Hydrierung der Schiff'schen Base aus DMAPA und Isobutyraldehyd zu N,N-Dimethyl-N'-isobutyl-propylendiamin.Catalytic hydrogenation of Schiff's base from DMAPA and isobutyraldehyde to N, N-dimethyl-N'-isobutyl-propylenediamine.
1 451 g (9,3 Mol) der Schiff'schen Base werden in einem 3-1 V4A-Autoklaven in Gegenwart von 10 Gew.-% Nickel-Katalysator (Zusammensetzung: etwa 52 Gew.-% Ni, Rest Kieselgur) bezogen auf die Schiff'sche Base bei 80 °C und 80 bar hydriert. Die Reaktionszeit beträgt 2 Stunden. Nach destillativer Aufarbeitung des Reaktionsproduktes erhält man 1 249 g (85 % d.Th) N,N-Dimethyl-N'- isobutyl-propylendiamin in einer Reinheit von > 98 %.1 451 g (9.3 mol) of the Schiff base are in a 3-1 V4A autoclave in the presence of 10 wt .-% nickel catalyst (composition: about 52 wt .-% Ni, the rest of diatomaceous earth) based on Schiff's base is hydrogenated at 80 ° C. and 80 bar. The response time is 2 hours. After working up the reaction product by distillation, 1,249 g (85% of theory) of N, N-dimethyl-N'-isobutyl-propylenediamine are obtained in a purity of> 98%.
Anlagerung von Ethylenoxid an N,N-Dimethyl-N'-isobutyl-propylendiamin zum N,N-Dimethyl-N'-isobutyl-N'-hydroxyethyl-propylendiamin.Addition of ethylene oxide to N, N-dimethyl-N'-isobutyl-propylenediamine to form N, N-dimethyl-N'-isobutyl-N'-hydroxyethyl-propylenediamine.
474 g (3 Mol) N,N-Dimethyl-N'-isobutyl-propylendiamin und 10 Gew.-%, bezogen auf das Propylendiamin, eines stark sauren Ionenaustauschers werden in einem 2,8 1-Autoklaven auf 130 °C erhitzt. Anschließend gibt man 145 g (3,3 Mol) Ethylenoxid über eine Feindosierpumpe zu. Während der Ethylenoxidzugabe und der anschließenden Nachreaktion soll die Temperatur zwischen 130 °C und 160 °C liegen. Bei höheren Temperaturen entstehen größere Anteile Nebenprodukte, die auf die Reaktion des Ethylenoxids mit sich selbst zurückzuführen sind. Nach beendeter Ethylenoxid-Zudosierung wird mittels Stickstoff ein Druck von 20 bar eingestellt. Unter diesen Bedingungen beläßt man den Reaktionsansatz noch 1 Std. Nach Beendigung der Nachreaktion wird das Reaktionsprodukt fraktioniert destilliert. Man erhält N,N-Dimethyl-N'-isobutyl-N'-ß-hydroxyethyl-propylendiamin in einer Ausbeute von 545 g (90 % d.Th.) und einer Reinheit von > 98 % als farblose, schwach nach Amin riechende Flüssigkeit mit folgenden physikalischen Eigenschaften:
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2940256 | 1979-10-04 | ||
| DE19792940256 DE2940256A1 (en) | 1979-10-04 | 1979-10-04 | N, N-DIMETHYL-N '- (BETA) -HYDROXYETHYL-PROPYLENE DIAMINE AND METHOD FOR PRODUCING THE SAME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0027209A1 true EP0027209A1 (en) | 1981-04-22 |
| EP0027209B1 EP0027209B1 (en) | 1983-10-12 |
Family
ID=6082696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80105942A Expired EP0027209B1 (en) | 1979-10-04 | 1980-10-01 | N,n-dimethyl-n'-isobutyl-n'-beta-hydroxyethyl 1,3-propylene diamine, and process for its preparation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4324918A (en) |
| EP (1) | EP0027209B1 (en) |
| JP (1) | JPS5812269B2 (en) |
| DE (2) | DE2940256A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0074537A1 (en) * | 1981-09-04 | 1983-03-23 | Ruhrchemie Aktiengesellschaft | N,N,N'-trimethyl-N'-2-hydroxyethyl-propylene diamine, process for its preparation, polyurethane containing 0,01 to 5% of N,N,N'-trimethyl-N'-2-hydroxyethyl propylene diamine and use of that amine as a catalyst |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430455A (en) * | 1981-03-09 | 1984-02-07 | Abbott Laboratories | N'-(2-Hydroxyalkyl)-N, N, N'-trimethyl-propylene diamines as catalysts for polyurethane foams |
| CA1254231A (en) * | 1984-12-03 | 1989-05-16 | Guido Sartori | Diaminoalcohols, their preparation and their use as acid gas removal agents |
| JP2519324B2 (en) * | 1989-08-23 | 1996-07-31 | 日本フリット株式会社 | Enamel board firing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2625684A1 (en) * | 1975-06-09 | 1976-12-30 | Air Prod & Chem | TERT. HYDROXYALKYLAMINE CATALYSTS FOR ISOCYANATE REACTIONS |
| EP0001616A2 (en) * | 1977-10-20 | 1979-05-02 | Ciba-Geigy Ag | Curable epoxy resin compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527804A (en) * | 1967-04-20 | 1970-09-08 | Universal Oil Prod Co | Hydroxyalkyl polysubstituted alkylene polyamines |
| US3428469A (en) * | 1968-03-06 | 1969-02-18 | Universal Oil Prod Co | Plastic and resin stabilized with borates of alkanolamines |
| US3925268A (en) * | 1973-04-23 | 1975-12-09 | Union Carbide Corp | Beta-amino nitrile catalysts for polyurethane preparation |
| US4101462A (en) * | 1977-04-07 | 1978-07-18 | Texaco Development Corp. | Urethane catalyst |
| US4255528A (en) * | 1979-09-24 | 1981-03-10 | Abbott Laboratories | Polyurethane process |
-
1979
- 1979-10-04 DE DE19792940256 patent/DE2940256A1/en not_active Withdrawn
-
1980
- 1980-09-25 JP JP55132420A patent/JPS5812269B2/en not_active Expired
- 1980-10-01 EP EP80105942A patent/EP0027209B1/en not_active Expired
- 1980-10-01 DE DE8080105942T patent/DE3065303D1/en not_active Expired
- 1980-10-03 US US06/193,697 patent/US4324918A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2625684A1 (en) * | 1975-06-09 | 1976-12-30 | Air Prod & Chem | TERT. HYDROXYALKYLAMINE CATALYSTS FOR ISOCYANATE REACTIONS |
| EP0001616A2 (en) * | 1977-10-20 | 1979-05-02 | Ciba-Geigy Ag | Curable epoxy resin compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0074537A1 (en) * | 1981-09-04 | 1983-03-23 | Ruhrchemie Aktiengesellschaft | N,N,N'-trimethyl-N'-2-hydroxyethyl-propylene diamine, process for its preparation, polyurethane containing 0,01 to 5% of N,N,N'-trimethyl-N'-2-hydroxyethyl propylene diamine and use of that amine as a catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3065303D1 (en) | 1983-11-17 |
| JPS5659740A (en) | 1981-05-23 |
| DE2940256A1 (en) | 1981-04-16 |
| JPS5812269B2 (en) | 1983-03-07 |
| EP0027209B1 (en) | 1983-10-12 |
| US4324918A (en) | 1982-04-13 |
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